JP2013505197A - Alumina titanate porous structure - Google Patents

Abstract

The present invention is based on the corresponding simple oxides, Al ₂ O ₃ , TiO ₂ , Fe ₂ O ₃ , Cr ₂ O ₃ , MnO ₂ , La ₂ O ₃ , Y ₂ O ₃ , Ga ₂ O. _At least one oxide of element M ₂ selected from the group comprising ₃ and at least one oxide of element M ₃ selected from the group comprising ZrO ₂ , Ce ₂ O ₃ , HfO ₂ , and optionally The present invention relates to a porous structure including an oxide ceramic material including at least one oxide of element M ₁ selected from MgO and CoO, and optionally SiO ₂ , and the material corresponds to a corresponding simple structure. It can be obtained by reactive sintering of an oxide or one of its precursors or by heat treatment of sintered particles having the composition.

Description

  The present invention relates to a porous structure such as a catalyst carrier or a granular medium filter, and relates to a porous structure in which the material constituting the part having the filter action and / or the active part is based on aluminum titanate. The ceramic material constituting the basic material of the ceramic filter or carrier according to the present invention is mainly composed of oxides of the elements Al and Ti. The porous structure usually has a honeycomb structure, and is used particularly in an exhaust pipe of a diesel type internal combustion engine.

In the following, the oxides containing said elements will be described with reference to the corresponding simple oxides, for example Al ₂ O ₃ or TiO ₂ , for convenience and according to the practice in the ceramic field. In particular, in the following description, unless stated otherwise, the proportions of the various elements constituting the oxides according to the invention are present in the chemical composition described by reference to the corresponding simple oxide weights. As a percentage by weight of the total oxides present.

  In the following, the application and advantages in a particular field of filter or catalyst carrier for removing pollutants contained in exhaust gas originating from gasoline or diesel internal combustion engines, to which the present invention relates, will be described. At present, all structures for purifying exhaust gases generally have a honeycomb structure.

  As is known, granular media filters are subjected to a series of stages during use, to perform the filter function (accumulating soot) and regenerating (removing soot). During the stage of performing the filter function, soot particles emitted by the engine are retained and deposited inside the filter. During the regeneration phase, soot particles are burned out inside the filter to restore its filter characteristics. Accordingly, it is understood that the mechanical strength properties of the material comprising the filter, both at low and high temperatures, are the most important for such applications. Similarly, the material is sufficiently stable to withstand the entire life of the vehicle to which it is attached, especially at temperatures that can rise slightly above 1000 ° C, if some regeneration steps are not well controlled. It must have a structure that is

  At present, filters are mainly made of porous ceramic materials, in particular silicon carbide or cordierite. This type of silicon carbide catalyst filter is, for example, European Patent Application Nos. 816065, 1142619, 1455923, or WO 2004/090294, 2004/065088. It is described in the issue pamphlet. Such filters are ideal for applications that filter out soot generated by heat engines, have excellent thermal conductivity, and have a porous character, especially average pore size and pore size distribution. It is possible to obtain an inert filter structure.

However, some of the disadvantages inherent to this material still remain, i.e., the first is due to the somewhat higher coefficient of thermal expansion of SiC, which is greater than 3 x ^10-6 K- ^1. Does not make it possible to produce large monolithic filters, and the filters are divided and bonded together using cement, for example as described in EP 1455923 Very often it is necessary to make several honeycomb elements. The second drawback, which is of economic nature, is generally above 2100 ° C. for sintering, ensuring sufficient thermomechanical strength of the honeycomb structure, especially during successive filter regeneration stages. This is due to the extremely high firing temperature. Such a temperature requires the installation of special equipment and considerably increases the cost of the final filter.

  From a different point of view, cordierite filters are known and have been used for a long time due to their low price, but at present, in such structures, the filter is locally above the melting point of cordierite. It is known that problems can occur during regeneration cycles with poor control that can be exposed to. The effects of these hot spots can range from partial loss of filter efficiency to complete destruction in the most severe cases. In addition, the cordierite chemical inertness is inadequate at the temperatures reached during the series of regenerations, so that it remains in the lubricant, fuel, oil and other residues that have accumulated in the structure during the stage of performing the filter function. It reacts with substances derived from things and is easily corroded by them, and this phenomenon can also cause the characteristics of the structure to deteriorate rapidly.

  The drawbacks as described above are described in, for example, WO 2004/011124 pamphlet, and in order to improve them, this literature describes aluminum titanate (60 to 60 wt.%) Reinforced with mullite (10 to 40 wt%). 90% by weight) is proposed as a filter with improved durability.

According to another aspect, according to EP 1 596 696, a honeycomb filter is obtained which is obtained by reactive sintering of aluminum oxide, titanium oxide and magnesium oxide between 1000 ° C. and 1700 ° C. It has been proposed to use a powder. The material obtained after sintering has two phases, namely, a main phase of Al ₂ TiO ₅ type of pseudo-plate titanite structure containing titanium, aluminum and magnesium, and Na _y K _1-y AlSi ₃ O ₈ type. It takes the form of a mixture of secondary feldspar phases.

  However, experiments conducted by the present applicant have shown that the performance of such structures based on porous materials of the aluminum titanate type, in particular for their direct use in high temperature applications, for example of granular media filters. It has been shown that it is difficult at present to guarantee the thermal stability and the coefficient of thermal expansion suitable for making it possible.

European Patent Application No. 816065 European Patent Application No. 1142619 European Patent Application No. 1455923 International Publication No. 2004/090294 Pamphlet International Publication No. 2004/065088 Pamphlet European Patent Application No. 1455923 International Publication No. 2004/011124 Pamphlet European Patent Application No. 1559696

  Thus, the object of the present invention has been substantially improved to make it more advantageous to use, in particular, the production of porous structures of filters and / or catalysts, generally honeycomb structures. It is to provide a porous structure containing an oxide material having the characteristics as described above.

More precisely, the present invention is a porous structure comprising a ceramic material, wherein the chemical composition of the ceramic material is expressed in wt% based on oxide,
More than 25% and less than 52% Al ₂ O ₃ ,
More than 26% and less than 55% TiO ₂ ,
At least one oxide of element M ₁ selected from MgO and CoO, less than 20% in total,
An element M ₂ selected from the group formed by Fe ₂ O ₃ , Cr ₂ O ₃ , MnO ₂ , La ₂ O ₃ , Y ₂ O ₃ and Ga ₂ O _{3 in} total greater than 1% and less than 20% At least one oxide of
At least one oxide of element M ₃ selected from the group formed by ZrO ₂ , Ce ₂ O ₃ and HfO _{2 in a} total of more than 1% and less than 25%,
Less than 20% SiO ₂ ,
And the composition is
Less than 10% MgO,
More than 1% and less than 20% Fe ₂ O ₃ ,
More than 1% and less than 10% ZrO ₂ ,
And the material is obtained by reaction sintering of the corresponding simple oxide or one of their precursors, or by heat treatment of sintered particles satisfying the above composition, The present invention relates to a porous structure containing a ceramic material.

As already explained, during the formulation, the proportions of the various elements constituting the oxide of the material are present in the chemical composition with reference to the corresponding simple oxide weight. It is expressed in wt% with respect to the total oxide. Nevertheless, in the context of the present invention, the elements M ₁ , M ₂ and M ₃ in the above relation are represented in the form of the corresponding simple oxides, which are traditional in solid state chemistry. They are usually present, at least in large part, in other more complex forms in the material according to the invention, and may be included in particular in mixed oxides, in particular aluminum titanate type It is clear that it may be included in the phase of

  Preferably, the porous structure is formed of the ceramic material.

Further, the porous structure according to the present invention is such that a′−t + 2m ₁ + m ₂ is between −6 and 6, expressed in mol% based on the total of oxides present in the composition. Satisfied composition, here
A is the content (mol%) of Al ₂ O ₃ ,
S is the SiO ₂ content (mol%),
A ′ = a−0.37 s
T is the content (mol%) of TiO ₂ ,
· M ₁ is the total content of oxides of M ₁ (mol%),
· M ₂ is the total content of oxides of M ₂ (mol%).

Preferably, Al ₂ O ₃ represents more than 30% of the chemical composition. Preferably, Al ₂ O ₃ represents less than 51% or less than 50% of the chemical composition, and the percentage content is given by weight based on the oxide.

Preferably, TiO ₂ is less than 50% or less than 45% of the chemical composition, and this percentage content is given by weight based on the oxide.

Preferably, when present, the oxide of M ₁ represents more than 1.5% of the chemical composition, very preferably more than 2%. Preferably, the M ₁ oxide represents less than 6% of the chemical composition, and these percentages are given by weight based on the oxide.

Preferably, M ₁ is exactly Mg.

Preferably, the M ₂ oxide represents more than 1.5% of the chemical composition, very preferably more than 2% and even more than 3%. Preferably, the M ₂ oxides together represent less than 20%, very preferably less than 15% of the chemical composition, and these percentages are given by weight based on the oxide.

Preferably, M ₂ is just Fe. Again preferably, in another embodiment, the element M ₂ comprises iron and lanthanum, provided that the content of Fe ₂ O ₃ remains greater than 1.0%, or even greater than 1.5%. You may comprise by the combination of these.

In such embodiments, Fe ₂ O ₃ (or the combined weight content of Fe ₂ O ₃ and La ₂ O ₃ species) is greater than 1% of the chemical composition, very preferably greater than 1.5%. It corresponds to. Preferably, Fe ₂ O ₃ (or the total weight content of Fe ₂ O ₃ + La ₂ O ₃ ) corresponds to less than 20%, very preferably less than 18%, or even less than 15% of the chemical composition, These percentages are given by weight based on the oxide.

In one embodiment, the composition comprises iron and magnesium, and optionally lanthanum. In this case, the corresponding oxides Fe ₂ O ₃ and MgO, and optionally La ₂ O ₃ , expressed in total weight, are greater than 1% of the chemical composition, even greater than 1.5%, Very preferably it corresponds to more than 2%. Preferably, Fe ₂ O ₃ and MgO, and optionally La ₂ O ₃ together represent less than 18%, very preferably less than 15% of the chemical composition, these percentages being oxides Is based on weight.

The oxides of M ₃ together represent more than 1% of the chemical composition, and this percentage is given by weight based on the oxide. Preferably, the M ₃ oxides together represent less than 10%, very preferably less than 8% of the chemical composition.

Preferably M ₃ is exactly Zr. Still preferably, as another embodiment, the element M ₃ may be composed of a combination of zirconium and cerium.

Therefore, in the composition of the above particles, according to this other preferred embodiment of the present invention, ZrO ₂ (M ₃ is Zr) is replaced by ZrO _2, provided that the ZrO ₂ content remains greater than 1%. And CeO ₂ (in this case, M ₃ is a combination of Zr and Ce). In such a case, for example, the material contains more than 1 wt% and less than 10 wt% (ZrO ₂ + CeO ₂ ), where (ZrO ₂ + CeO ₂ ) is the sum of the contents by weight of the two oxides in the composition It is.

  Needless to say, in the context of the description herein, the composition may nevertheless contain other compounds in the form of inevitable impurities. In particular, even if only one zirconium-containing reactant is initially introduced into the process for producing the structure according to the present invention, the reactant usually contains a small amount of hafnium in the form of inevitable impurities. It is known to contain, sometimes up to 1 or 2 mol% of the total amount of zirconium introduced.

For example, the material may be expressed in wt% based on oxide in the following chemical composition: more than 35% and less than 50% Al ₂ O ₃ , more than 26% and less than 50% TiO ₂ , less than 6%. It can have MgO, more than 2% and less than 15% Fe ₂ O ₃ , more than 2% and less than 8% ZrO ₂ , and more than 0.5% and less than 15% SiO ₂ .

In addition to the content by weight of all the oxides present, the structure according to the invention may also contain other trace elements. In particular, the structure may contain silicon in an amount between 0.1 wt% and 20 wt% based on the corresponding oxide SiO ₂ . For example, SiO ₂ is more than 0.1% of the chemical composition, in particular more than 0.5% or more than 1%, otherwise more than 2%, actually more than 3% or more than 5%. Equivalent to. For example, SiO ₂ represents less than 18% of the chemical composition, in particular less than 15%, alternatively less than 12% or less than 10%, these percentages being given by the weight based on the oxide.

The porous structure may contain other elements such as boron, Ca, Sr, Na, K, Ba type alkali metals or alkaline earth metals, the total amount of these elements present being Based on the corresponding oxides B ₂ O ₃ , CaO, SrO, Na ₂ O, K ₂ O, BaO in addition to the content by weight of all oxides corresponding to the elements present in the porous structure And preferably less than 10 wt%, such as less than 5 wt%, or less than 4 wt%, or less than 3 wt%. The percentage content of each trace element based on the weight of the corresponding oxide is, for example, less than 4%, or less than 3%, or less than 1%.

According to one possible embodiment of the invention, the porous structure according to the invention, expressed in wt% based on oxide, has the following chemical composition:
More than 25% and less than 52% Al ₂ O ₃ ,
More than 26% and less than 55% TiO ₂ ,
More than 1% and less than 20% Fe ₂ O ₃ ,
Less than 20% SiO ₂ ,
Less than 10% MgO or less than 2% MgO,
More than 1% and less than 10% ZrO ₂ and, optionally, a total of more than 2% and less than 13% B ₂ O ₃ , CaO, Na ₂ O, K ₂ O, SrO and BaO At least one oxide selected from the group;
Have

In the above chemical composition, Fe ₂ O ₃ may be replaced with the same ratio as the combination of Fe ₂ O ₃ and La ₂ O ₃ .

Similarly, according to another embodiment that can be combined with what has been described so far, in the above chemical composition, ZrO ₂ may be replaced with the same ratio as the combination of ZrO ₂ and CeO ₂ .

According to another possible embodiment of the invention, the porous structure according to the invention, expressed in wt% based on oxide, has the following chemical composition:
More than 35% and less than 51% Al ₂ O ₃ , for example between 38% and 50% Al ₂ O ₃ ,
More than 26% and less than 45% TiO ₂ ,
More than 1% and less than 20% Fe ₂ O ₃ or a combination of (Fe ₂ O ₃ + La ₂ O ₃ ),
If desired, more than 0.1% and less than 20% SiO ₂ ;
Less than 2% MgO or less than 1% MgO,
More than 1% and less than 10% ZrO ₂ and, optionally, a total of more than 2% and less than 13% B ₂ O ₃ , CaO, Na ₂ O, K ₂ O, SrO and BaO At least one oxide selected from the group;
Have

In the above chemical composition, Fe ₂ O ₃ may be replaced with the same ratio as the combination of Fe ₂ O ₃ and La ₂ O ₃ .

Similarly, according to another embodiment that can be combined with what has been described so far, in the above chemical composition, ZrO ₂ may be replaced with the same ratio as the combination of ZrO ₂ and CeO ₂ .

Such chemical composition is expressed in wt% based on oxide,
Between 1% and 18% Fe ₂ O ₃ or (Fe ₂ O ₃ + La ₂ O ₃ ),
Between 3% and 18% SiO ₂ , and between 1% and 8% ZrO ₂ or (ZrO ₂ + CeO ₂ ),
It is preferable to have.

  In order not to make the description herein unnecessarily redundant, not all possible combinations according to the invention between the various preferred embodiments of the composition of the material according to the invention described above are reported. However, of course, all possible combinations of the first and / or preferred values and ranges described above can be envisioned, and they are described by the applicant in the description herein. Must be considered (especially a combination of two, three or more).

The porous structure according to the present invention further comprises a solid solution type oxide containing at least one element selected from titanium, aluminum, M ₂ , at least one element selected from M ₃ , and optionally an element selected from M ₁ . A phase, at least one phase consisting essentially of titanium oxide TiO ₂ and / or zirconium oxide ZrO ₂ and / or cerium oxide CeO ₂ and / or hafnium oxide HfO ₂ , and optionally at least one silicate phase; Can be mainly included or formed by them.

Preferably, the porous structure according to the invention consists essentially of a solid solution type oxide phase comprising titanium, aluminum, iron, zirconium and optionally magnesium and titanium oxide TiO ₂ and / or zirconium oxide ZrO _2. At least one phase and, if desired, at least one silicate phase can mainly be included or formed therewith.

  The silicate phase described above can be present in a proportion that can range from 0 to 45% of the total weight of the material. In general, the silicate phase consists mainly of silica and alumina, and the weight ratio of silica in the silicate phase is greater than 34%.

According to another possible embodiment,
Al ₂ O ₃ can correspond between 48 wt% and 54 wt%,
TiO ₂ can correspond between 35 wt% and 48 wt%, for example between 38 wt% and 45 wt%,
Fe ₂ O ₃ or (Fe ₂ O ₃ + La ₂ O ₃ ) can correspond between 1 wt% and 8 wt%, for example between 2 wt% and 6 wt%,
-SiO ₂ is present in a proportion of less than 1 wt% or less than 0.5 wt%,
ZrO ₂ (or ZrO ₂ + CeO ₂ ) is less than 3 wt%,
MgO can correspond between 1 wt% and 8 wt%, for example between 2 wt% and 6 wt%.

  The material constituting the porous structure according to the present invention can be obtained by any technique commonly used in the art.

  According to the first variant embodiment, the material making up the structure may be obtained directly in the usual manner, simply mixing the initial reactants in the appropriate ratio to obtain the desired composition, and then You may obtain by heating and making it react in a solid state (reaction sintering).

The reactants can be, for example, simple oxides Al ₂ O ₃ , TiO ₂ and, if desired, other oxides of the elements easily present in the structure, for example in the form of a solid solution. . According to the invention, it is also possible to use any precursor of the oxide, for example in the form of carbonates, hydroxides or other organometallic compounds of the above elements. The term “precursor” often decomposes into the corresponding simple oxide at a stage prior to heat treatment, ie generally at temperatures below 1000 ° C., alternatively below 800 ° C., and even below 500 ° C. It is understood to mean a substance.

  According to another method for producing the structure according to the invention, the reactants are sintered particles corresponding to the chemical composition described above and obtained from the simple oxides described above. Presinter the mixture of initial reactants, that is, allow a simple oxide to react to form sintered particles containing at least one main phase of an aluminum titanate type structure Heat to the temperature you want. According to this embodiment, it is also possible to use the aforementioned oxide precursors. Again, as described above, the precursor is sintered to form a sintered particle that mainly comprises at least one phase having an aluminum titanate type structure. Heat to a temperature that allows it to react.

  One method for producing such a structure according to the present invention is generally as follows. That is, first, the initial reactants are mixed in an appropriate ratio to obtain the desired composition.

  As is well known in the art, this process generally involves mixing an initial mixture of reactants with a methylcellulose type organic binder and pore former, such as starch, graphite, polyethylene, PMMA, and the like, and Gradually adding water until the fluidity necessary to enable the process of extruding the honeycomb structure is obtained.

  For example, during this first step, the initial mixture is mixed with 1-30 wt% of at least one pore former selected according to the desired pore size and then at least one organic fluidization. Add agent and / or organic binder and water.

  This mixing results in a homogeneous product in the form of a paste. The process of extruding this product through a suitably shaped die allows a honeycomb shaped monolith to be obtained using well known techniques. In this case, the method can include, for example, a step of drying the resulting monolith. During this drying step, the resulting green ceramic monolith is usually sufficient by microwave drying or heat drying to bring the content of chemically unbound water to less than 1 wt%. Let dry for hours. If it is desired to obtain a particulate media filter, the method can further include the step of closing any other flow path at each end of the monolith.

  The step of firing the integral part in which the filter part is based on aluminum titanate is in principle carried out at a temperature above 1300 ° C. and not exceeding 1800 ° C., preferably not exceeding 1750 ° C. This temperature is adjusted in particular depending on the other phases and / or oxides present in the porous material. Usually, during the firing step, the monolithic structure is heated to a temperature between 1300 ° C. and 1600 ° C. in an atmosphere containing oxygen or an inert gas.

  One advantage of the present invention is that, unlike SiC filters (as described above), it is possible to obtain a monolithic structure with very large dimensions without the need for splitting, but it is less preferred. However, according to one embodiment, the method optionally assembles a plurality of integral parts into a combined filter structure using known techniques such as those described in EP-A-816065. The process of carrying out may be included.

  The filter structure made of the porous ceramic material according to the invention is preferably of the honeycomb type. It has a preferred porosity of greater than 10%, generally between 20% and 70%, or between 30% and 60%, and the average pore size is determined by mercury porosimetry on a Micromeritics 9500 instrument. Measured, ideally between 5 and 60 μm, in particular between 10 and 20 μm.

  Such filter structures generally have a central portion that includes a number of adjacent channels or passages of parallel axes separated by a wall formed of a porous material.

  In a particulate media filter, the flow paths are defined to define an inlet chamber that opens to the gas inlet surface and an outlet chamber that opens to the gas discharge surface so that the gas passes through the porous wall. One or the other end is closed by a plug.

The present invention also generally comprises at least one noble metal such as Pt and / or Rh and / or Pd from the structures defined above, and optionally such as CeO ₂ , ZrO ₂ or CeO ₂ —ZrO ₂ . It also relates to a filter or catalyst support, obtained by depositing, preferably impregnating, at least one active catalyst phase comprising oxide, supported or preferably unsupported. The catalyst carrier also has a honeycomb structure, but the flow path is not closed with a plug, and the catalyst is deposited in the pores of the flow path.

  The invention and its advantages are better understood on reading the following non-limiting examples. In these examples, unless stated otherwise, all percentage contents are given by weight.

In these examples, samples were made from the following raw materials. These raw materials are
Almatis CL4400FG alumina containing 99.8% Al ₂ O _{3 and} having a median diameter d ₅₀ of about 5.2 μm,
-TRONOX T-R titanium oxide containing 99.5% TiO _{2 and} having a diameter of about 0.3 μm,
Elchem Microsilica Grade 971U SiO _{2 with} a purity of 99.7%,
Fe ₂ O _{3 with} a purity higher than 98%,
Lime containing about 97% CaO and having a particle diameter of more than 80% less than 80 μm,
· Societe des Produits Chimiques Harbonnieres marketed by, strontium carbonate containing more than a SrCO ₃ 98.5%,
Zirconium oxide with a purity higher than 98.5% and a median diameter d ₅₀ of 3.5 μm, marketed under the name CC10 by the company Saint-Gobain ZirPro,
Lanthanum oxide La ₂ O _{3 with} a purity higher than 99%,
Cerium oxide containing about 99% CeO _{2 and} having an average particle size of less than 20 μm,
It is.

  A sample according to the present invention and a sample for comparison were obtained from the above reactants mixed at an appropriate ratio.

  More precisely, the initial reactant mixture was mixed and then pressed into a cylindrical shape and then they were sintered in air at the temperatures shown in Table 1 for 4 hours.

  Next, the produced sample was analyzed. Table 1 shows the results of analysis performed for each sample of each example.

In Table 1,
1) The chemical composition expressed in wt% based on oxide was measured by fluorescent X-ray.
2) The characteristics of the crystalline phase present in the refractory product were examined by X-ray diffraction and microprobe analysis EPMA (electron beam microanalysis). Based on the results thus obtained, the weight percentage of each phase and its composition could be estimated. In Table 1, AT indicates an aluminum titanate type oxide solid solution (main phase), PS indicates the presence of a silicate phase, the other phases indicate the presence of at least one other minor phase P2, “˜” means that the phase is present in the form of a trace.
3) The stability of the crystalline phase present was measured in a test which consists in comparing the initially present crystalline phase with that present after heat treatment at 1100 ° C. for 100 hours by X-ray diffraction. A product is considered stable when the maximum intensity of the main peak corresponding to the appearance of corundum Al ₂ O ₃ after this treatment remains below 50% of the average of the maximum intensity of the three main peaks of the AT phase. And was considered very stable if it remained below 30% (such products are labeled “yes” in Table 1).
4) Compressive strength (R) was measured at room temperature by compressing the prepared sample at a speed of 1 mm / min with an LLOYD facility equipped with a 10 kN load cell.
5) The density was measured by an ordinary technique (Archimedes method). The porosity shown in Table 1 corresponds to the difference between the theoretical density (the predicted maximum density of a non-porous material measured by the helium specific gravity method for the pulverized product) and the measured density as a percentage.

  From the data in Table 1, it can be seen that the combination of porosity characteristics and mechanical strength characteristics is improved. That is, for the same sintering temperature, this table shows that the porosity of the example according to the invention can be compared with that of the comparative example. At the same time, as shown in Table 1, the examples according to the present invention have a strength R that is significantly greater than that of the comparative examples.

As described above, the product of the present invention can be used according to the requirements.
To obtain better properties in relation to the desired composition of the material at a given sintering (firing) temperature,
-Or adjusting the high porosity level of the material (especially by adding a pore former to the initial reactants) while maintaining good mechanical integrity,
Enable.

Claims (12)

A porous structure formed of an oxide ceramic material, the oxide ceramic material expressed in wt% based on oxide, and having the following composition:
More than 25% and less than 52% Al ₂ O ₃ ,
More than 26% and less than 55% TiO ₂ ,
At least one oxide of element M ₁ selected from MgO and CoO, less than 20% in total,
An element M ₂ selected from the group formed by Fe ₂ O ₃ , Cr ₂ O ₃ , MnO ₂ , La ₂ O ₃ , Y ₂ O ₃ and Ga ₂ O _{3 in} total greater than 1% and less than 20% At least one oxide of
At least one oxide of element M ₃ selected from the group formed by ZrO ₂ , Ce ₂ O ₃ and HfO _{2 in a} total of more than 1% and less than 25%,
Less than 20% SiO ₂ ,
Satisfied, the composition is
Less than 10% MgO,
More than 1% and less than 20% Fe ₂ O ₃ ,
More than 1% and less than 10% ZrO ₂ ,
And the material is obtained by reaction sintering of the corresponding simple oxide or one of their precursors, or obtained by heat treatment of the sintered particles, the composition of which In terms of mole percent based on all oxides present in the composition, a′−t + 2m ₁ + m ₂ is such that it is between −6 and 6,
A is the content of Al ₂ O ₃ in mol%,
S is the content of SiO ₂ in mol%,
A ′ = a−0.37 s
T is the content in mole percent of TiO ₂
M ₁ is the total content in mole% of M ₁ oxide,
M ₂ is the total content of M ₂ oxide in mol%,
A porous structure formed of an oxide ceramic material. The porous structure according to claim 1, wherein M ₃ is selected from Zr or a combination of Zr and Ce, and the content of ZrO ₂ in the material is more than 0.7%. The porous structure according to claim 1 or 2, wherein M ₁ is Mg, M ₂ contains Fe or Fe, and M ₃ contains Zr or Zr. The porous structure according to claim 1, wherein M ₂ is composed of a combination of iron and lanthanum. The porous structure according to claim 1, wherein M ₃ is composed of a combination of zirconium and cerium. The material, expressed as wt% based on oxide, has the following chemical composition:
More than 25% and less than 52% Al ₂ O ₃ ,
More than 26% and less than 55% TiO ₂ ,
Less than 10% MgO,
More than 1% and less than 20% Fe ₂ O ₃ or (Fe ₂ O ₃ + La ₂ O ₃ ),
More than 1% and less than 10% ZrO ₂ or (ZrO ₂ + CeO ₂ ),
Less than 20% SiO ₂ ,
The porous structure according to claim 1, comprising: The material, expressed as wt% based on oxide, has the following chemical composition:
More than 35% and less than 50% Al ₂ O ₃ ,
More than 26% and less than 50% TiO ₂ ,
Less than 6% MgO,
More than 2% and less than 15% Fe ₂ O ₃ or (Fe ₂ O ₃ + La ₂ O ₃ ),
More than 2% and less than 8% ZrO ₂ or (ZrO ₂ + CeO ₂ ),
More than 0.5% and less than 15% SiO ₂ ,
The porous structure according to claim 6, comprising: Including many SiO ₂ than 1%, preferably a number of SiO ₂ than 3%, preferably from many SiO ₂ than 5%, porous structure according to one of claims 1 to 7. The material comprises titanium, aluminum, iron, zirconium, and optionally a magnesium-containing main phase consisting of a solid solution type phase and at least one phase consisting essentially of titanium oxide TiO ₂ and / or zirconium oxide ZrO _2. And, optionally, at least one silicate phase.   The porous structure of claim 9, wherein the silicate phase is present in a proportion that can range from 0 to 45% of the total weight of the material.   The porous structure according to claim 10, wherein the silicate phase is mainly composed of silica and alumina, and the weight ratio of silica in the silicate phase is larger than 34%.   It has a honeycomb type structure, and is a catalyst carrier or filter especially for automobile applications. The ceramic material constituting the structure has a porosity of more than 10%, and the pore size centers are 5 μm and 60 μm. The porous structure according to claim 1, which is between